U.S. patent application number 13/054550 was filed with the patent office on 2011-05-26 for ethylene oligomerization catalyst and use thereof.
This patent application is currently assigned to MITSUI CHEMICALS, INC.. Invention is credited to Phala Heng, Koji Inoue, Teruo Muraishi.
Application Number | 20110124938 13/054550 |
Document ID | / |
Family ID | 41570339 |
Filed Date | 2011-05-26 |
United States Patent
Application |
20110124938 |
Kind Code |
A1 |
Inoue; Koji ; et
al. |
May 26, 2011 |
ETHYLENE OLIGOMERIZATION CATALYST AND USE THEREOF
Abstract
Ethylene is oligomerized with a catalyst in which nickel is
supported on a support containing silica and alumina. The catalyst
has little deterioration over long periods and affords oligomers
with high productivity. The ethylene oligomerization catalyst
includes a support and a nickel compound supported on the support,
the support including silica and alumina, and the amount of nickel
supported is in the range of 0.0001 to 1 wt % based on the weight
of the support, and the molar ratio of silica to alumina in the
support (SiO.sub.2/Al.sub.2O.sub.3) is in the range of 100 to 2000.
In a process of the invention, ethylene is oligomerized with use of
the catalyst.
Inventors: |
Inoue; Koji; (Chiba, JP)
; Muraishi; Teruo; (Kanagawa, JP) ; Heng;
Phala; (Kanagawa, JP) |
Assignee: |
MITSUI CHEMICALS, INC.
Minato-ku, Tokyo
JP
|
Family ID: |
41570339 |
Appl. No.: |
13/054550 |
Filed: |
July 22, 2009 |
PCT Filed: |
July 22, 2009 |
PCT NO: |
PCT/JP2009/063075 |
371 Date: |
January 17, 2011 |
Current U.S.
Class: |
585/533 ;
502/259 |
Current CPC
Class: |
Y02P 20/584 20151101;
C07C 2523/755 20130101; B01J 38/14 20130101; B01J 37/035 20130101;
C07C 6/04 20130101; C07C 2/10 20130101; Y02P 20/52 20151101; B01J
23/755 20130101; B01J 23/94 20130101; C07C 6/04 20130101; C07C
2521/12 20130101; C07C 11/02 20130101 |
Class at
Publication: |
585/533 ;
502/259 |
International
Class: |
C07C 2/02 20060101
C07C002/02; B01J 21/12 20060101 B01J021/12 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 23, 2008 |
JP |
2008-189759 |
Claims
1. An ethylene oligomerization catalyst comprising a support and a
nickel compound supported on the support, the support containing
silica and alumina, wherein: the amount of nickel supported is in
the range of 0.0001 to 1 wt % based on the weight of the support,
and the molar ratio of silica to alumina in the support
(SiO.sub.2/Al.sub.2O.sub.3) is in the range of 100 to 2000.
2. The ethylene oligomerization catalyst according to claim 1,
wherein the molar ratio of nickel to aluminum in the catalyst
(Ni/Al) is in the range of 0.00005 to 1.5.
3. The ethylene oligomerization catalyst according to claim 1,
wherein the amount of nickel supported is in the range of 0.0001 to
0.5 wt % based on the weight of the support, and the molar ratio of
silica to alumina in the support (SiO.sub.2/Al.sub.2O.sub.3) is in
the range of 100 to 1000.
4. The ethylene oligomerization catalyst according to claim 1,
wherein the molar ratio of silica to alumina in the support
(SiO.sub.2/Al.sub.2O.sub.3) is in the range of 150 to 1000.
5. The ethylene oligomerization catalyst according to claim 1,
wherein the molar ratio of nickel to aluminum in the catalyst
(Ni/Al) is in the range of 0.00005 to 1.2.
6. The ethylene oligomerization catalyst according to claim 1,
wherein the amount of nickel supported is in the range of 0.0001 to
less than 0.1 wt % based on the weight of the support.
7. A process for producing ethylene oligomers, comprising
oligomerizing ethylene in the presence of the oligomerization
catalyst of claim 1.
8. A process for producing ethylene oligomers, comprising
oligomerizing ethylene at a temperature of 100 to 400.degree. C.
and a pressure of 0.1 to 50 MPa with the oligomerization catalyst
of claim 1.
9. The process according to claim 8, wherein the temperature is in
the range of 150 to 350.degree. C. and the pressure is in the range
of 0.1 to 10 MPa.
10. A process for producing olefins, comprising performing an
oligomerization reaction by contacting ethylene with the
oligomerization catalyst of claim 1, and successively performing a
disproportionation reaction by contacting the oligomers from the
oligomerization reaction with ethylene in the presence of a
disproportionation catalyst.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to ethylene oligomerization
catalysts and uses thereof. In more detail, the invention relates
to catalysts in which nickel is supported on a support including
silica and alumina and the support has a large molar ratio of
silica to alumina (SiO.sub.2/Al.sub.2O.sub.3) and supports a very
small amount of nickel, and which have ethylene oligomerization
activity, in particular ethylene dimerization activity. The present
invention also relates to ethylene oligomerization processes and
olefin production processes using the catalysts.
BACKGROUND OF THE INVENTION
[0002] Liquid phase olefin oligomerization using catalysts
consisting of a titanium or nickel complex and an alkylaluminum has
been known. This oligomerization process, however, entails
separating and recovering the catalysts and is thus complicated.
Olefin oligomerization is also known to be performed by a liquid
phase or gas phase process with use of catalysts in which nickel is
supported on a support composed of silica, alumina, silica and
alumina, or the like.
[0003] Patent Document 1 discloses catalysts wherein 0.1 to 5 wt %
of nickel is supported on a support composed of silica and alumina
(alumina content: 1 to 10 wt %). The silica/alumina molar ratio
(SiO.sub.2/Al.sub.2O.sub.3) is calculated to range from 15 to 168.
It is described therein that the catalytic activity is not enhanced
if the alumina content is less than 1 wt %, namely, if the
silica/alumina molar ratio (SiO.sub.2/Al.sub.2O.sub.3) exceeds
168.
[0004] Patent Documents 2 to 5 disclose catalysts obtained by
coprecipitation of nickel, silica and alumina; catalysts obtained
by supporting nickel on a silica/alumina support through
impregnation cycles; and catalysts obtained by adding ammonium
hydroxide to a nickel nitrate solution to obtain ammoniacal nickel
and impregnating a silica/alumina support with the nickel. The
nickel content in these catalysts is 2 wt % or more.
[0005] Patent Document 6 discloses catalysts wherein the nickel
oxide/silica molar ratio is 0.001 or more and the silica/alumina
molar ratio (SiO.sub.2/Al.sub.2O.sub.3) ranges from 30 to 500. The
nickel content is described to be 0.092 wt % or more. Preferred
embodiments and working examples disclose 0.021 as a nickel
oxide/silica molar ratio, and the nickel content is calculated
therefrom to be 1.7 wt %.
[0006] Further, the catalysts of Patent Documents 2 to 6 have a
problem of short life under high temperature reaction conditions.
Furthermore, the catalysts of Patent Documents 1 to 6 easily
decrease catalytic activity and induce isomerization to afford
branched oligomers of low utility value.
[0007] Patent Document 7 discloses that a catalyst supporting
nickel on a silica/alumina support is reacted with a
sulfur-containing compound to afford a catalyst which supports
nickel and sulfur on the support. However, the catalysts supporting
nickel and sulfur show inferior activity to catalysts which support
nickel alone.
[0008] Non-Patent Document 1 discloses catalysts wherein nickel is
supported on a silica/alumina coprecipitated support by ion
exchange. The catalysts are described to catalyze ethylene
oligomerization under conditions such that the ethylene conversion
is high at 90% or more. However, such high conversion conditions
lead to an increased molecular weight of the oligomer due to
successive reactions, and it is impossible to obtain low molecular
oligomers such as dimers. Further, the catalysts permit long
operation at a reaction temperature of 108.degree. C., but a slight
increase in reaction temperature to 127.degree. C. causes
irreversible deactivation. [0009] Patent Document 1: U.S. Pat. No.
2,581,228 [0010] Patent Document 2: U.S. Pat. No. 2,921,971 [0011]
Patent Document 3: U.S. Pat. No. 2,949,429 [0012] Patent Document
4: U.S. Pat. No. 3,045,054 [0013] Patent Document 5: U.S. Pat. No.
2,904,608 [0014] Patent Document 6: WO 93/06926 [0015] Patent
Document 7: U.S. Pat. No. 3,527,839 [0016] Non-Patent Document 1:
J. Haveling, C. P. Nicolaides, M. S. Scurrell, Catalysts and
conditions for the highly efficient, selective and stable
heterogeneous oligomerization of ethylene, ELSEVIER, Applied
Catalysis A, 1998 Vol. 173, pp. 1-9
SUMMARY OF THE INVENTION
[0017] It is an object of the invention to provide catalysts in
which a nickel compound is supported on a support containing silica
and alumina, and which is capable of catalyzing oligomerization of
ethylene to achieve high productivity for a long term with little
catalyst deterioration.
[0018] The present inventors studied diligently to solve the
problems in the art as described hereinabove. They have then found
that catalysts have small deterioration and can afford oligomers
with high productivity when a very small amount of nickel is
supported on a silica/alumina support which has a very low alumina
content, that is, has a large molar ratio of silica to alumina
(SiO.sub.2/Al.sub.2O.sub.3). The present invention has been
completed based on the finding.
[0019] The present inventors worked hard in order to invent
catalysts that show little deterioration over a long term and can
produce oligomers with high productivity, and have found out a
catalytic performance mechanism as follows.
[0020] Nickel works as a catalyst in the oligomerization of
ethylene. However, when the nickel content is high as described in
Patent Documents 2 to 6, nickel is aggregated and lowers activity
and therefore a long catalyst life cannot be obtained. In
particular, the nickel aggregation is facilitated under high
temperature reaction conditions and is a critical factor that
decreases the catalytic activity and life.
[0021] To enhance the catalytic activity and life, it is important
to highly disperse nickel on a support as well as to stabilize
nickel on the support. In the supports containing silica and
alumina, alumina contributes to the stabilization of nickel. As
long as the alumina content is small, the catalytic activity and
catalyst life increase with increasing alumina content. When the
alumina content is or is more than a certain level, however, the
catalytic activity and life are lowered. In detail, a high alumina
content corresponds to many acid sites on the catalyst surface.
Cokes are accumulated at the acid sites on the catalyst surface,
and the catalysts decrease catalytic activity and many acid sites
induce isomerization to afford branched oligomers of low utility
value.
[0022] The catalysts described in Patent Documents 1 to 6 have a
small SiO.sub.2/Al.sub.2O.sub.3 ratio, namely a high alumina
content. Their acidic properties evoke undesired reactions such as
coke generation and isomerization to afford branched oligomers, and
cause lower catalytic activity and catalyst life.
[0023] It is therefore desired that the alumina content should be
reduced to the minimum necessary. Meanwhile, alumina on the support
stabilizes nickel, and therefore nickel stabilization is difficult
when the molar number of nickel in the catalyst is in excess over
that of alumina. It is thus preferred that the nickel/aluminum
molar ratio (Ni/Al) in the catalyst is not far above 1. According
to the invention, a very small amount of nickel is supported on a
silica/alumina support which has a very low content of alumina,
that is, has a large molar ratio of silica to alumina
(SiO.sub.2/Al.sub.2O.sub.3); whereby nickel is highly dispersed on
the support stably and is less liable to aggregate. As a result,
the catalysts according to the invention have little deterioration,
high activity and long life.
[0024] The present invention is concerned with the following [1] to
[10].
[0025] [1] An ethylene oligomerization catalyst comprising a
support and a nickel compound supported on the support, the support
containing silica and alumina, wherein:
[0026] the amount of nickel supported is in the range of 0.0001 to
1 wt % based on the weight of the support, and the molar ratio of
silica to alumina in the support (SiO.sub.2/Al.sub.2O.sub.3) is in
the range of 100 to 2000.
[0027] [2] The ethylene oligomerization catalyst described in [1],
wherein the molar ratio of nickel to aluminum in the catalyst
(Ni/Al) is in the range of 0.00005 to 1.5.
[0028] [3] The ethylene oligomerization catalyst described in [1]
or [2], wherein the amount of nickel supported is in the range of
0.0001 to 0.5 wt % based on the weight of the support, and the
molar ratio of silica to alumina in the support
(SiO.sub.2/Al.sub.2O.sub.3) is in the range of 100 to 1000.
[0029] [4] The ethylene oligomerization catalyst described in any
one of [1] to [3], wherein the molar ratio of silica to alumina in
the support (SiO.sub.2/Al.sub.2O.sub.3) is in the range of 150 to
1000.
[0030] [5] The ethylene oligomerization catalyst described in any
one of [1] to [4], wherein the molar ratio of nickel to aluminum in
the catalyst (Ni/Al) is in the range of 0.00005 to 1.2.
[0031] [6] The ethylene oligomerization catalyst described in any
one of [1] to [5], wherein the amount of nickel supported is in the
range of 0.0001 to less than 0.1 wt % based on the weight of the
support.
[0032] [7] A process for producing ethylene oligomers, comprising
oligomerizing ethylene in the presence of the oligomerization
catalyst of any one of [1] to [6].
[0033] [8] A process for producing ethylene oligomers, comprising
oligomerizing ethylene at a temperature of 100 to 400.degree. C.
and a pressure of 0.1 to 50 MPa with the oligomerization catalyst
of any one of [1] to [6].
[0034] [9] The process described in [8], wherein the temperature is
in the range of 150 to 350.degree. C. and the pressure is in the
range of 0.1 to 10 MPa.
[0035] [10] A process for producing olefins, comprising performing
an oligomerization reaction by contacting ethylene with the
oligomerization catalyst of any one of [1] to [6], and successively
performing a disproportionation reaction by contacting the
oligomers from the oligomerization reaction with ethylene in the
presence of a disproportionation catalyst.
ADVANTAGEOUS EFFECTS OF THE INVENTION
[0036] The catalysts of the invention are suited for ethylene
oligomerization, are easily synthesized, and involve very small
amounts of metals thereby providing economic advantages. The
ethylene oligomerization processes with the catalysts of the
invention can selectively synthesize, for example, 1-butene or
1-hexene from ethylene. 1-Butene and 1-hexene are useful comonomers
for the production of polyethylenes, and butene is a useful
material for the synthesis of propylene by disproportionation
reaction with ethylene. The presence of isobutene with a branched
structure is not preferable in the disproportionation reaction. The
catalysts according to the invention permit selective synthesis of
linear butenes.
[0037] The oligomerization processes with the catalysts of the
invention enable long-term oligomer production with little catalyst
deterioration and with high productivity.
[0038] The oligomerization catalysts according to the invention are
resistant to deterioration over a long term even under high
temperature reaction conditions. The olefin production processes of
the invention involve a combination of the oligomerization catalyst
with a disproportionation catalyst and thereby afford target
olefins with high productivity. For example, ethylene is
oligomerized into butene with the oligomerization catalyst, and the
butene is reacted with unreacted ethylene in the presence of a
disproportionation catalyst to afford propylene efficiently.
BRIEF DESCRIPTION OF THE DRAWING
[0039] FIG. 1 is a graph showing changes with time of ethylene
conversion and selectivity for butenes in the reaction in Example
23.
PREFERRED EMBODIMENTS OF THE INVENTION
Ethylene Oligomerization Catalysts
[0040] Ethylene oligomerization catalysts according to the
invention comprise a support containing silica and alumina, and a
nickel compound supported on the support.
[0041] The amount of nickel supported is in the range of 0.0001 to
1 wt %, preferably 0.0001 to 0.5 wt %, more preferably 0.0001 to
0.13 wt %, and still more preferably 0.0001 to less than 0.1 wt %,
based on the weight of the support. If the amount of nickel
supported is below this range, oligomerization activity tends to be
greatly lowered. If the nickel amount exceeds the above range,
nickel is aggregated during the reaction and lowers oligomerization
activity, and therefore the catalysts tend to fail ensure stable
productivity over a long term.
[0042] The molar ratio of silica to alumina in the support
(SiO.sub.2/Al.sub.2O.sub.3) is in the range of 100 to 2000,
preferably 100 to 1000, and more preferably 150 to 1000. If the
silica/alumina molar ratio (SiO.sub.2/Al.sub.2O.sub.3) is below
this range, the catalysts have an increased number of acid sites
and tend to afford a higher proportion of branched olefins, and
cokes are accumulated on the catalyst surface to possibly lower the
catalytic activity. If the silica/alumina molar ratio
(SiO.sub.2/Al.sub.2O.sub.3) exceeds the above range, a sufficient
amount of alumina required to stabilize nickel cannot be ensured,
and the catalysts tend to decrease oligomerization catalytic
activity and catalyst life.
[0043] The molar ratio of nickel to aluminum in the catalyst
(Ni/Al) is preferably in the range of 0.00005 to 1.5, more
preferably 0.00005 to 1.2, and still more preferably 0.0005 to 1.0.
If the nickel/aluminum molar ratio (Ni/Al) is below this range, the
catalysts tend to fail to have sufficient catalytic activity. If
the nickel/aluminum molar ratio (Ni/Al) exceeds the above range, a
sufficient amount of alumina required to stabilize nickel cannot be
ensured, and the catalytic activity and catalyst life tend to be
lowered by nickel aggregation.
[0044] The supports in the invention are not limited as long as
they contain silica and alumina and the silica/alumina molar ratio
(SiO.sub.2/Al.sub.2O.sub.3) is in the foregoing range.
[0045] The catalysts of the invention may be synthesized by various
methods without limitation as long as the amount of nickel
supported on the support is in the specified range. Preferably, the
catalysts synthesized have a nickel/aluminum molar ratio (Ni/Al) in
the above-described range.
[0046] Exemplary catalyst synthesizing processes include the
following processes (i) to (vi):
[0047] Process (i) Coprecipitation from a solution containing a
silica source compound, an alumina source compound and a nickel
compound is carried out. The resultant precipitate is then filtered
off, washed, dried and calcined.
[0048] Process (ii) Silica is impregnated with a solution of an
alumina source compound and a nickel compound, and the solvent is
distilled off. The residue is then dried and calcined.
[0049] Process (iii) A silica gel is mixed with a solution of an
alumina source compound and a nickel compound, and the solvent is
distilled off. The residue is then dried and calcined.
[0050] Process (iv) Silica is impregnated with a solution of an
alumina source compound, and the solvent is distilled off. The
residue is then dried and calcined. A nickel compound is supported
on the calcined product by impregnation or ion exchange, followed
by drying and calcination.
[0051] Process (v) A nickel compound is supported on a support
containing silica and alumina by impregnation or ion exchange,
followed by drying and calcination.
[0052] Process (vi) Nickel is supported on a support containing
silica and alumina by CVD.
[0053] When the synthesis methods involve impregnation, the
impregnation may be performed in one step or a plurality of
steps.
[0054] The silica/alumina molar ratio (SiO.sub.2/Al.sub.2O.sub.3)
may be controlled to fall in the foregoing range by adjusting the
amount of the alumina source compound relative to the mole number
of silica calculated from the weight of the material silica in the
above synthesis methods. Similarly, the nickel/aluminum molar ratio
(Ni/Al) may be controlled to fall in the foregoing range by
adjusting the amount of the nickel compound relative to the mole
number of the alumina source compound.
[0055] The shapes of the catalysts in the invention are not
particularly limited, and catalysts in various shapes may be used.
The supports containing silica and alumina from the precipitation
method are fine powders. A nickel compound may be supported on such
powdery catalyst, or a nickel compound may be supported after the
support containing silica and alumina is shaped.
[0056] Examples of the silica source compounds include silicates
such as sodium silicate and alkoxysilanes, although not
particularly limited thereto.
[0057] Examples of the alumina source compounds include aluminum
nitrate and aluminum hydroxide, although not particularly limited
thereto.
[0058] Examples of the nickel compounds include nickel acetate,
nickel nitrate, nickel sulfate, nickel carbonate, nickel hydroxide,
nickel halides, nickel acetylacetonate complexes and nickel
phosphine complexes, although not particularly limited thereto. The
nickel compounds may be used singly, or two or more kinds may be
used in combination. Nickel nitrate and nickel sulfate are
preferred. Specific examples of the nickel compounds include nickel
nitrate hydrate and nickel sulfate hydrate.
[0059] The drying temperature in the synthesis methods is
preferably in the range of 70 to 150.degree. C., and more
preferably 80 to 130.degree. C. The drying time is preferably in
the range of 0.1 to 50 hours, and more preferably 0.5 to 20 hours.
The calcination temperature is preferably in the range of 200 to
800.degree. C., and more preferably 200 to 700.degree. C. The
calcination time is preferably in the range of 0.1 to 300 hours,
and more preferably 0.5 to 150 hours. This calcination time ensures
that the catalyst life is increased while maintaining catalytic
activity.
[0060] In the invention, silica supports having a high specific
surface area and a high pore volume are preferably used. The
specific surface area is preferably in the range of 200 to 1200
m.sup.2/g, and the pore volume is preferably in the range of 0.4 to
2 cc/g. If these parameters are below these ranges, the obtainable
catalysts tend to fail to show sufficient catalytic activity and
catalyst life. If these parameters exceed the above ranges, the
catalyst strength is insufficient and industrial use tends to be
difficult. Silica supports having these properties may be
conventional amorphous silicas, or may be mesoporous silicas such
as MCM-41 and MCM-48 or zeolites with large pore diameters such as
Y-zeolites, X-zeolites, mordenite, .beta.-zeolites, L-zeolites and
MFI.
[0061] Silicas may be commercially available or may be synthesized
by carrying out precipitation from a solution containing a silica
source, and filtering, drying and calcining the precipitate. When
silicates such as sodium silicate are used, the precipitate may be
washed with a solution containing an ammonium salt such as ammonium
nitrate to substitute the sodium ions with ammonium ions and may be
thereafter dried and calcined. The drying temperature is in the
range of 70 to 150.degree. C., and preferably 80 to 130.degree. C.
The calcination temperature is in the range of 200 to 800.degree.
C., and preferably 200 to 700.degree. C.
[0062] Supports containing silica and alumina may also be
synthesized by admixing a solution of an alumina source compound to
a silica gel, distilling off the solvent, and drying and calcining
the residue. Supports may be alternatively prepared by impregnating
the silica obtained by the above-described method with a solution
of an alumina source compound, then distilling off the solvent, and
drying and calcining the residue. The drying temperature is in the
range of 70 to 150.degree. C., and preferably 80 to 130.degree. C.
The calcination temperature is in the range of 200 to 800.degree.
C., and preferably 200 to 700.degree. C.
[0063] Still alternatively, supports may be prepared by
coprecipitating silica and alumina from a mixture of a silica
source compound and an alumina source compound, and filtering,
drying and calcining the precipitate. The drying temperature is in
the range of 70 to 150.degree. C., and preferably 80 to 130.degree.
C. The calcination temperature is in the range of 200 to
800.degree. C., and preferably 200 to 700.degree. C.
[0064] Still alternatively, commercially available silica/alumina
may be dealuminated into silica/alumina having a larger
SiO.sub.2/Al.sub.2O.sub.3 ratio. Exemplary dealumination methods
include vapor treatment, silicon tetrachloride treatment and
hexafluorosilicate treatment as described in Catalysis and
Zeolites, Fundamentals and Applications (edited by J. Weitkamp and
L. Puppe, Springer, 1999), pp. 127-155.
[0065] When the silica source compound contains an alumina source
compound as an impurity, the silica source compound may be
precipitated, filtered, dried and calcined; and the resulting
compound may be used as a support containing silica and alumina, or
alumina may be added thereto by the methods described
hereinabove.
[0066] In a preferred embodiment in view of simple catalyst
synthesis, commercially available silica may be impregnated with a
solution of an alumina source compound, then the solvent may be
distilled off and the residue may be dried and calcined, and
thereafter nickel is supported on the calcined product by
impregnating the calcined product with a nickel compound solution
or by ion exchange.
<Processes for Producing Ethylene Oligomers>
[0067] In the processes for producing ethylene oligomers according
to the present invention, ethylene is oligomerized with the
oligomerization catalyst as described hereinabove.
[0068] In the ethylene oligomerization processes, raw material
ethylene may contain paraffins, oxygen-containing compounds or
water together. The raw material ethylene may be diluted with an
inert gas such as helium, nitrogen or argon.
[0069] The oligomerization catalysts can efficiently catalyze the
oligomerization reaction of ethylene into ethylene oligomers.
[0070] The ethylene oligomers produced by the processes of the
invention include, for example, 1-butene, cis-2-butene,
trans-2-butene, 3-methyl-1-pentene, 3-methyl-2-pentene,
4-methyl-1-pentene, 4-methyl-2-pentene, 1-hexene, 2-hexene,
3-hexene, 3,4-dimethyl-3-hexene, 3-methyl-3-heptene, 1-octene,
2-octene, 3-octene and 4-octene.
[0071] In the ethylene oligomerization processes, the ethylene
oligomerization reaction may be performed with reactors of any
types such as fixed bed reactors, fluidized bed reactors or moving
bed reactors. Fixed bed reactors are preferable because of simple
equipment. The oligomerization catalyst is packed in such reactors
and ethylene is fed thereto and oligomerized.
[0072] The shapes of the oligomerization catalysts used in the
ethylene oligomerization processes are not particularly limited,
and catalysts in various shapes may be used. When the catalyst is
fine powder, it may be packed in the fixed bed reactor directly or
after physically mixed with a filler that is inert in the
oligomerization reaction such as silica balls or alumina balls to
avoid heavy pressure loss. Alternatively, fine powder of catalyst
may be compacted, or may be shaped after kneaded with a sintering
agent (a binder) that does not alter the catalytic performance.
[0073] Typical sintering agents are silica sintering agents,
further alumina sintering agents, titania sintering agents,
zirconia sintering agents or diatomaceous earth sintering agents
may also be used. The sintering is preferably performed at
temperatures of 500 to 800.degree. C. Exemplary shapes include
tablets, extrusions, pellets, spheres, microspheres, CDS
extrusions, trilobes, quadlobes, rings, two-spoke rings, special
spoke rings such as HGS, EW and LDP, rib rings and granules.
[0074] In the ethylene oligomerization processes, ethylene is
oligomerized with the foregoing oligomerization catalyst generally
at a temperature of 100 to 400.degree. C. and a pressure of 0.1 to
50 MPa.
[0075] The oligomerization temperature is not particularly limited,
but is generally in the range of 100 to 400.degree. C., preferably
130 to 400.degree. C., and more preferably 150 to 350.degree. C. If
the reaction temperature is below this range, by-products such as
high-molecular oligomers will not smoothly diffuse away from the
catalyst surface and the catalyst life tends to be reduced. If the
reaction temperature exceeds the above range, nickel on the
catalyst is aggregated and coke generation is accelerated, so that
the lowering in catalytic activity tends to be accelerated.
[0076] In a preferred embodiment, the catalyst is activated prior
to the reaction by supplying an inert gas such as helium, nitrogen
or argon into the heated reactor. The heating temperature is in the
range of 100 to 600.degree. C., and preferably 200 to 500.degree.
C. The heating time ranges from 0.1 to 10 hours, and preferably 1
to 5 hours.
[0077] After the catalyst is activated with an inert gas, it may be
further treated with raw material ethylene or a reducing gas such
as hydrogen. The treatment temperature is in the range of 200 to
600.degree. C., and preferably 300 to 600.degree. C. The treatment
time ranges from 0.1 to 20 hours, and preferably 0.1 to 10 hours.
This treatment increases the catalyst life without deteriorating
the catalytic activity.
[0078] The pressure in the oligomerization reaction is not
particularly limited, but is generally in the range of 0.1 to 50
MPa, preferably 0.1 to 10 MPa, and more preferably 0.1 to 5 MPa. If
the pressure is below this range, establishing a highly efficient
process tends to be difficult. A pressure exceeding the above range
tends to cause an increased amount of by-products.
[0079] The weight hourly space velocity (WHSV) of ethylene per unit
catalyst weight is preferably in the range of 0.1 to 50 h.sup.-1,
more preferably 0.5 to 40 h.sup.-1, and still more preferably 0.5
to 30 h.sup.-1. If the WHSV is below this range, the productivity
tends to be lowered and successive oligomerization reactions take
place progressively possibly to lower the selectivity for dimers or
trimers. If the WHSV exceeds the above range, the ethylene
conversion tends to be lowered.
[0080] A single reactor or a plurality of reactors may be used. In
the case of plural reactors, a parallel arrangement of the reactors
allows for constant production by switching oligomerization
reaction in one reactor and catalyst regeneration in other
reactor.
[0081] The reaction product may be separated and purified from
unreacted ethylene or high-boiling oligomers by known methods such
as distillation, extraction and adsorption. The unreacted ethylene
may be recycled to the reactor.
[0082] To regenerate the catalyst, for example, the supply of
ethylene is suspended, the reactor is purged with an inert gas such
as helium, nitrogen or argon, and an inert gas such as helium,
nitrogen or argon that contains 0.1 to 20% by volume of oxygen is
passed through the reactor at 300 to 700.degree. C., preferably 400
to 600.degree. C. for 0.1 to 100 hours, preferably 0.5 to 50 hours.
The gas flow rate may be in the range of 1 to 100 ml/min, and
preferably 10 to 80 ml/min.
[0083] The ethylene oligomerization catalysts of the invention may
be effectively used also for the dimerization of ethylene. The
ethylene dimerization may be carried out under the conditions as
described hereinabove, but dimers may be produced with high
selectivity when the reaction is performed under conditions such
that the ethylene conversion will be lower than in usual
oligomerization reactions. For example, such lower ethylene
conversion may be achieved by controlling the amount of nickel
supported on the oligomerization catalyst.
<Olefin Production Processes>
[0084] In the processes for producing olefins according to the
invention, an oligomerization reaction is carried out by contacting
ethylene with the oligomerization catalyst as described above, and
successively a disproportionation reaction is conducted by
contacting the oligomer from the oligomerization reaction with
ethylene in the presence of a disproportionation catalyst.
[0085] According to the olefin production processes of the
invention, ethylene as a raw material may be converted efficiently
and economically into an olefin having a different number of carbon
atoms from the raw material ethylene (hereinafter, resultant
olefin).
[0086] The resultant olefins produced by the processes of the
invention include, for example, propylene, 1-butene, cis-2-butene,
trans-2-butene, 1-pentene, 2-pentene, 3-methyl-1-butene,
2-methyl-1-butene and 2-methyl-2-butene.
[0087] The olefin production processes use the foregoing
oligomerization catalysts that have little deterioration over long
periods even under high temperature oligomerization conditions.
Hence, the oligomerization reaction in the olefin production
processes may be generally carried out at 100 to 400.degree. C.,
and are preferably performed under high temperature conditions such
as 130 to 400.degree. C., and more preferably 150 to 350.degree.
C.
[0088] The disproportionation catalysts used in the olefin
production processes are not particularly limited, and known such
catalysts may be used with examples including catalysts disclosed
in U.S. Pat. No. 4,575,575. Cocatalysts may be used in combination
with the disproportionation catalysts. The cocatalysts are not
particularly limited, and cocatalysts disclosed in U.S. Pat. No.
4,575,575 may be used.
[0089] The disproportionation temperature may be for example as
described in U.S. Pat. No. 4,575,575. Industrial disproportionation
reactions are generally carried out under high temperature
conditions such as 260.degree. C. or above (e.g., J. C. Mol,
Industrial applications of olefin metathesis, ELSEVIER, Journal of
Molecular Catalysis A: Chemical, 2004, Vol. 213, pp. 39-45).
[0090] In the olefin production processes, the oligomerization
catalysts permit the oligomerization reaction to be performed at
high temperatures. The resultant oligomer at a high temperature is
successively brought into contact with the unreacted raw material
ethylene in the presence of the disproportionation catalyst,
whereby the heating energy required for the disproportionation
reaction can be reduced to the minimum necessary. Therefore, the
olefin production processes of the invention efficiently and
economically provide target resultant olefins from ethylene as raw
material.
[0091] In the disproportionation of the olefin from the processes
for producing ethylene oligomers of the invention and unreacted
ethylene, the ethylene oligomerization and the subsequent
disproportionation reaction may be carried out in the same or
differing reactors. When they are conducted in the same reactor,
the oligomerization catalyst and the disproportionation catalyst
may be continually packed in the reactor or may have a filler
therebetween that is inert in the oligomerization and
disproportionation reactions such as quartz sand. The reaction
temperature is generally in the range of 100 to 400.degree. C.,
preferably 130 to 400.degree. C., and more preferably 150 to
350.degree. C. The reaction pressure is preferably in the range of
0.1 to 50 MPa, and more preferably 0.1 to 10 MPa.
[0092] When the ethylene oligomerization reaction and the
disproportionation reaction are carried out in respective reactors,
the oligomerization catalyst is packed in an oligomerization
reactor and ethylene is oligomerized therein, and the resultant
oligomer and unreacted ethylene are fed to a disproportionation
reactor containing the disproportionation catalyst, thereby
producing resultant olefin. Where necessary, a step for removing
by-products other than the oligomer and unreacted ethylene may be
performed between the ethylene oligomerization reaction and the
disproportionation reaction. In performing the disproportionation
reaction, raw material ethylene may be added to the unreacted
ethylene. The oligomer from the oligomerization reaction may be
purified by known methods such as distillation, extraction and
adsorption and may be supplied to the disproportionation reactor
together with raw material ethylene.
[0093] The ethylene oligomerization temperature is generally in the
range of 100 to 400.degree. C., preferably 130 to 400.degree. C.,
and more preferably 150 to 350.degree. C.; and the reaction
pressure is preferably in the range of 0.1 to 50 MPa, and more
preferably 0.1 to 10 MPa. The disproportionation temperature and
pressure are not particularly limited, and may be as described in
U.S. Pat. No. 4,575,575.
[0094] The ethylene oligomerization reaction and the
disproportionation reaction in respective reactors may be each
carried out under optimum conditions.
[0095] The product from the disproportionation reaction may be
separated and purified from unreacted ethylene and oligomers from
the oligomerization by known methods such as distillation,
extraction and adsorption. The unreacted ethylene may be recycled
to the oligomerization reaction or the disproportionation reaction.
The oligomers from the oligomerization reaction may be recycled to
the disproportionation reaction.
[0096] In the oligomerization and disproportionation reactions, the
raw material ethylene may contain hydrogen gas as described in
British Patent No. 1117968.
EXAMPLES
[0097] The present invention will be described in greater detail
hereinbelow without limiting the scope of the invention.
[0098] The amount of nickel supported and the silica/alumina molar
ratio (SiO.sub.2/Al.sub.2O.sub.3) were determined quantitatively
with an ICP emission spectrometer (VISTA-PRO manufactured by Seiko
Instruments Inc.), an ICP mass spectrometer (Agilent 7500s
manufactured by Agilent Technologies Inc.) or an atomic absorption
photometer (Z-5000 manufactured by Hitachi, Ltd.). Unreacted raw
materials and reaction products were quantified by gas
chromatography.
[0099] The catalyst life was defined as the time until the initial
ethylene conversion lowered 10%.
Example 1
(1) Preparation of Support
[0100] 0.0525 g of aluminum hydroxide and 1.0 g of sodium hydroxide
were added to 1.5 ml of distilled water and were heated under
reflux to give a transparent aqueous solution. Additional 50 ml of
distilled water was added, and the mixture was heated with stirring
to form a homogeneous aqueous solution. To the aqueous solution,
there were added an aqueous solution of 55.7 g of water glass (No.
3) in 217 ml of distilled water, and 110 ml of 1.4 M nitric acid.
The mixture was vigorously stirred at room temperature and was aged
for 3 days. Thereafter, the solid was filtered and was washed with
water.
[0101] The solid was added to 300 ml of a 1 M aqueous ammonium
nitrate solution. The mixture was stirred at 50.degree. C. for 1
hour and was aged at room temperature overnight. The solid formed
was filtered, washed with water, dried at 80.degree. C. in air for
18 hours, and calcined at 500.degree. C. for 3 hours to afford
13.26 g of a support containing silica and alumina.
(2) Preparation of Catalyst
[0102] 2.0 g of the support obtained in (1) above was suspended in
20 ml of distilled water. Subsequently, 20 ml of an aqueous
solution containing 0.044 g of nickel nitrate hexahydrate was added
to the suspension, followed by stirring at room temperature for 1
hour and heating at 80.degree. C. for 20 hours. The temperature was
lowered to room temperature, and the solid formed was filtered,
washed with water, dried at 80.degree. C. in air for 3 hours, and
calcined at 500.degree. C. for 6 hours to afford a catalyst.
[0103] The catalyst was found to contain 0.13 wt % of nickel
relative to the support weight and have a silica/alumina molar
ratio (hereinafter, also SiO.sub.2/Al.sub.2O.sub.3) of 640 and a
nickel/aluminum molar ratio (hereinafter, also Ni/Al) of 0.50.
Properties of the catalyst obtained are set forth in Table 1.
(3) Oligomerization Reaction
[0104] A fixed bed flow reactor (stainless steel, inner diameter:
9.5 mm, length: 250 mm) was used. The fixed bed flow reactor was
packed with 0.300 g of the catalyst obtained in (2) above, together
with quartz wool and quartz sand as holding materials, so that the
total length of the packings became 250 mm. Nitrogen was passed
through the reactor at a rate of 50 ml/min at atmospheric pressure,
and the catalyst layer was held at 300.degree. C. for 2 hours. The
gas flow was changed from nitrogen to ethylene, which was fed at
300.degree. C., 0.1 MPa and WHSV of 6.13 h.sup.-1, and thereby
ethylene was oligomerized. After the reaction for 24 hours, the
ethylene conversion was 19.8%, the selectivity for butenes was
84.6%, and the selectivity for hexenes was 9.2%. The catalyst life
was 24 hours. The results are set forth in Table 2.
Example 2
[0105] A catalyst was prepared in the same manner as in Example 1,
except that the amount of the support obtained in Example 1 (1) was
changed from 2.0 g to 1.0 g, and that 0.044 g of nickel nitrate
hexahydrate was replaced by 0.020 g of nickel sulfate hexahydrate.
Properties of the catalyst are set forth in Table 1. Reaction was
performed as described in Example 1 (3), except that the above
catalyst was used. After the reaction for 24 hours, the ethylene
conversion was 20.0%, the selectivity for butenes was 84.0%, and
the selectivity for hexenes was 9.6%. The catalyst life was 53
hours. The results are set forth in Table 2.
Example 3
[0106] A catalyst was prepared in the same manner as in Example 2,
except that 0.020 g of nickel sulfate hexahydrate was replaced by
0.018 g of nickel chloride hexahydrate. Properties of the catalyst
are set forth in Table 1. Reaction was performed as described in
Example 1 (3), except that the above catalyst was used. After the
reaction for 24 hours, the ethylene conversion was 19.1%, the
selectivity for butenes was 84.3%, and the selectivity for hexenes
was 9.4%. The catalyst life was 30 hours. The results are set forth
in Table 2.
Example 4
[0107] A catalyst was prepared in the same manner as in Example 1,
except that 0.044 g of nickel nitrate hexahydrate was replaced by
0.038 g of nickel acetate tetrahydrate. Properties of the catalyst
are set forth in Table 1. Reaction was performed as described in
Example 1 (3), except that the above catalyst was used. After the
reaction for 24 hours, the ethylene conversion was 18.0%, the
selectivity for butenes was 84.5%, and the selectivity for hexenes
was 9.3%. The catalyst life was 20 hours. The results are set forth
in Table 2.
Example 5
(1) Preparation of Support
[0108] 2.8 g of CARIACT G130 pellets (manufactured by FUJI SILYSIA
CHEMICAL LTD.) were suspended in 11 ml of distilled water, and 2.8
ml of an aqueous solution containing 0.07 g of aluminum nitrate
nonahydrate was added to the suspension. The mixture was stirred at
room temperature for 10 minutes, and water was distilled away at
70.degree. C. under reduced pressure. The solid thus formed was
dried at 80.degree. C. in air for 3 hours and was calcined at
500.degree. C. for 6 hours to afford a support containing silica
and alumina.
(2) Preparation of Catalyst
[0109] 2.0 g of the support obtained in (1) above was suspended in
20 ml of distilled water. Subsequently, 20 ml of an aqueous
solution containing 0.0044 g of nickel nitrate hexahydrate was
added to the suspension, followed by stirring at room temperature
for 10 minutes and heating at 80.degree. C. for 20 hours. The
temperature was lowered to room temperature, and the solid formed
was filtered, washed with water, dried at 80.degree. C. for 3
hours, and calcined at 300.degree. C. for 6 hours to afford a
catalyst.
[0110] The catalyst was found to contain 0.038 wt % of nickel
relative to the support weight and have SiO.sub.2/Al.sub.2O.sub.3
of 621 and Ni/Al of 0.13. Properties of the catalyst obtained are
set forth in Table 1.
(3) Oligomerization Reaction
[0111] Reaction was performed as described in Example 1 (3), except
that the catalyst obtained in (2) above was used. After the
reaction for 28 hours, the ethylene conversion was 29.2%, the
selectivity for butenes was 86.4%, and the selectivity for hexenes
was 8.9%. The catalyst life was 70 hours. The results are set forth
in Table 2.
Example 6
(1) Preparation of Support
[0112] 3.0 g of CARIACT Q-6 (manufactured by FUJI SILYSIA CHEMICAL
LTD.) was suspended in 12 ml of distilled water, and 3 ml of an
aqueous solution containing 0.075 g of aluminum nitrate nonahydrate
was added to the suspension. The mixture was stirred at room
temperature for 10 minutes, and water was distilled away at
70.degree. C. under reduced pressure. The solid thus formed was
dried at 80.degree. C. in air for 3 hours and was calcined at
500.degree. C. for 6 hours to afford a support containing silica
and alumina.
(2) Preparation of Catalyst
[0113] 2.0 g of the support obtained in (1) above was suspended in
20 ml of distilled water. Subsequently, 20 ml of an aqueous
solution containing 0.0044 g of nickel nitrate hexahydrate was
added to the suspension, followed by stirring at room temperature
for 10 minutes and heating at 80.degree. C. for 20 hours. The
temperature was lowered to room temperature, and the solid formed
was filtered, washed with water, dried at 80.degree. C. in air for
3 hours, and calcined at 300.degree. C. for 6 hours to afford a
catalyst.
[0114] Properties of the catalyst obtained are set forth in Table
1.
(3) Oligomerization Reaction
[0115] Reaction was performed as described in Example 1 (3), except
that the catalyst obtained in (2) above was used. The results after
the reaction for 24 hours are set forth in Table 2.
Example 7
(1) Preparation of Support
[0116] 5.0 g of Sylosphere 1504 (manufactured by FUJI SILYSIA
CHEMICAL LTD.) was suspended in 20 ml of distilled water, and 5 ml
of an aqueous solution containing 0.125 g of aluminum nitrate
nonahydrate was added to the suspension. The mixture was stirred at
room temperature for 10 minutes, and water was distilled away at
70.degree. C. under reduced pressure. The solid thus formed was
dried at 80.degree. C. in air for 3 hours and was calcined at
500.degree. C. for 6 hours to afford a support containing silica
and alumina.
(2) Preparation of Catalyst
[0117] 2.0 g of the support obtained in (1) above was suspended in
20 ml of distilled water. Subsequently, 20 ml of an aqueous
solution containing 0.0022 g of nickel nitrate hexahydrate was
added to the suspension, followed by stirring at room temperature
for 10 minutes and heating at 80.degree. C. for 20 hours. The
temperature was lowered to room temperature, and the solid formed
was filtered, washed with water, dried at 80.degree. C. in air for
3 hours, and calcined at 300.degree. C. for 6 hours to afford a
catalyst.
[0118] The catalyst was found to contain 0.02 wt % of nickel
relative to the support weight and have SiO.sub.2/Al.sub.2O.sub.3
of 532 and Ni/Al of 0.07. Properties of the catalyst obtained are
set forth in Table 1.
(3) Oligomerization Reaction
[0119] A fixed bed flow reactor (stainless steel, inner diameter:
9.5 mm, length: 250 mm) was used. The fixed bed flow reactor was
packed with 0.275 g of the catalyst obtained in (2) above, together
with quartz wool and quartz sand as holding materials, so that the
total length of the packings became 250 mm. Nitrogen was passed
through the reactor at a rate of 50 ml/min at atmospheric pressure,
and the catalyst layer was held at 300.degree. C. for 2 hours. The
temperature of the catalyst layer was lowered to 250.degree. C.,
and the gas flow was changed from nitrogen to ethylene, which was
fed at 250.degree. C., 0.35 MPa and WHSV of 6.67 h.sup.-1, and
thereby ethylene was oligomerized. After the reaction for 24 hours,
the ethylene conversion was 21.8%, the selectivity for butenes was
89.9%, and the selectivity for hexenes was 8.0%. The catalyst life
was 310 hours. The results are set forth in Table 2.
Comparative Example 1
[0120] A catalyst was prepared in the same manner as in Example 1,
except that aluminum hydroxide was not used. Properties of the
catalyst are set forth in Table 1. Reaction was performed as
described in Example 1 (3), except that the above catalyst was
used. The results after the reaction for 24 hours are set forth in
Table 2. Ethylene did not undergo the reaction. This result was
probably due to a high Ni/Al ratio of 6.13.
Comparative Example 2
[0121] 1.0 g of .gamma.-alumina (manufactured by Sumitomo Chemical
Co., Ltd.) was suspended in 10 ml of distilled water, and 2.5 ml of
an aqueous solution containing 0.055 g of nickel sulfate
hexahydrate was added to the suspension. The mixture was stirred at
room temperature for 10 minutes, and water was distilled away. The
solid thus formed was dried at 110.degree. C. in air for 3 hours
and was continuously dried at the temperature for 1 hour in an
atmosphere purged with nitrogen. Thereafter, the solid was calcined
at 510.degree. C. for 16 hours in the nitrogen atmosphere to afford
a catalyst. Properties of the catalyst obtained are set forth in
Table 1. Reaction was performed as described in Example 1 (3),
except that the above catalyst was used. The results after the
reaction for 18 hours are set forth in Table 2. Ethylene did not
undergo the reaction. This result was probably due to an extremely
low Ni/Al ratio.
Comparative Example 3
[0122] 97 ml of an aqueous solution containing 2.80 g of nickel
nitrate hexahydrate was added to 10 g of ZSM-5 (NH.sub.4 type,
manufactured by ZEOLYST, SiO.sub.2/Al.sub.2O.sub.3=50), followed by
stirring at room temperature for 5 minutes and heating at
80.degree. C. for 5 hours. The temperature was lowered to room
temperature, and the solid formed was filtered, washed with water,
dried at 120.degree. C. in air for 4 hours, and calcined at
500.degree. C. for 6 hours to afford a catalyst. Properties of the
catalyst obtained are set forth in Table 1. Reaction was performed
as described in Example 1 (3), except that the above catalyst was
used. After the reaction for 27 hours, the ethylene conversion was
11.5%, the selectivity for butenes was 31.3%, and the selectivity
for hexenes was 14.9%. The catalyst life was 3 hours. The results
are set forth in Table 2. The low catalytic activity in Comparative
Example 3 was probably due to a low SiO.sub.2/Al.sub.2O.sub.3
ratio.
Comparative Example 4
(1) Preparation of Support
[0123] 0.9 g of aluminum hydroxide and 1.0 g of sodium hydroxide
were added to 1.5 ml of distilled water and were heated under
reflux to give a transparent aqueous solution. Additional 50 ml of
distilled water was added, and the mixture was heated with stirring
to form a homogeneous aqueous solution. To the aqueous solution,
there were added an aqueous solution of 55.7 g of water glass (No.
3) in 217 ml of distilled water, and 110 ml of 1.4 M nitric acid.
The mixture was vigorously stirred at room temperature and was aged
for 3 days. Thereafter, the solid was filtered and was washed with
water.
[0124] The solid was added to 500 ml of a 1 M aqueous ammonium
nitrate solution. The mixture was stirred at 50.degree. C. for 1
hour and was aged at room temperature overnight. The solid formed
was filtered, washed with water, dried at 80.degree. C. in air for
18 hours, and calcined at 550.degree. C. for 3 hours to afford 16.8
g of a support containing silica and alumina.
(2) Preparation of Catalyst
[0125] 2.0 g of the support obtained in (1) above was suspended in
20 ml of distilled water. Subsequently, 20 ml of an aqueous
solution containing 0.044 g of nickel nitrate hexahydrate was added
to the suspension, followed by stirring at room temperature for 10
minutes. Water was distilled away at 70.degree. C. under reduced
pressure. The solid formed was dried at 80.degree. C. for 18 hours
and was calcined at 500.degree. C. for 6 hours to afford a
catalyst. Properties of the catalyst obtained are set forth in
Table 1.
(3) Oligomerization Reaction
[0126] Reaction was performed as described in Example 1 (3), except
that the catalyst obtained in (2) above was used. After the
reaction for 27 hours, the ethylene conversion was 23.2%, the
selectivity for butenes was 83.3%, and the selectivity for hexenes
was 10.0%. The catalyst life was 6 hours. The results are set forth
in Table 2. The low catalytic activity in Comparative Example 4 was
probably due to a low SiO.sub.2/Al.sub.2O.sub.3 ratio.
TABLE-US-00001 TABLE 1 Amount of nickel SiO.sub.2/Al.sub.2O.sub.3
Ni/Al supported (wt %) (mol/mol) (mol/mol) Ex. 1 0.13 640 0.50 Ex.
2 0.11 650 0.39 Ex. 3 0.11 590 0.36 Ex. 4 0.16 547 0.57 Ex. 5 0.038
621 0.13 Ex. 6 0.042 487 0.13 Ex. 7 0.02 532 0.07 Comp. 0.40 2177
6.13 Ex. 1 Comp. 0.18 0 <0.0005 Ex. 2 Comp. 0.17 50 0.05 Ex. 3
Comp. 0.44 37 0.11 Ex. 4
TABLE-US-00002 TABLE 2 Reac- Reac- Eth- Selec- Selec- tion tion
ylene tivity tivity temper- pres- con- for for ature sure WHSV
version butenes hexenes Life (.degree. C.) (MPa) (h.sup.-1) (%) (%)
(%) (h) Ex. 1 300 0.1 6.13 19.8 84.6 9.2 24 Ex. 2 300 0.1 6.13 20.0
84.0 9.6 53 Ex. 3 300 0.1 6.13 19.1 84.3 9.4 30 Ex. 4 300 0.1 6.13
18.0 84.5 9.3 20 Ex. 5 300 0.1 6.13 29.2.sup.1) 86.4.sup.1)
8.9.sup.1) 70 Ex. 6 300 0.1 6.13 28.5 86.4 9.0 70 Ex. 7 250 0.35
6.67 21.8 89.9 8.0 310 Comp. 300 0.1 6.13 0 -- -- -- Ex. 1 Comp.
300 0.1 6.13 0.sup.2) -- -- -- Ex. 2 Comp. 300 0.1 6.13 11.5.sup.3)
31.3.sup.3) 14.9.sup.3) 3 Ex. 3 Comp. 300 0.1 6.13 23.2 83.3 10.0 6
Ex. 4 .sup.1)Date after the reaction for 28 hours .sup.2)Data after
the reaction for 18 hours .sup.3)Data after the reaction for 27
hours
Example 8
(1) Preparation of Support
[0127] 5.0 g of CARIACT Q-6 (manufactured by FUJI SILYSIA CHEMICAL
LTD.) was suspended in 20 ml of distilled water, and 5 ml of an
aqueous solution containing 0.125 g of aluminum nitrate nonahydrate
was added to the suspension. The mixture was stirred at room
temperature for 10 minutes, and water was distilled away at
70.degree. C. under reduced pressure. The solid thus formed was
dried at 80.degree. C. in air for 3 hours and was calcined at
500.degree. C. for 6 hours to afford a support containing silica
and alumina.
(2) Preparation of Catalyst
[0128] 2.0 g of the support obtained in (1) above was suspended in
20 ml of distilled water. Subsequently, 20 ml of an aqueous
solution containing 0.0044 g of nickel nitrate hexahydrate was
added to the suspension, followed by stirring at room temperature
for 1 hour and heating at 80.degree. C. for 20 hours. The
temperature was lowered to room temperature, and the solid formed
was filtered, washed with water, dried at 80.degree. C. in air for
3 hours, and calcined at 300.degree. C. for 6 hours to afford a
catalyst.
[0129] The catalyst was found to contain 0.038 wt % of nickel
relative to the support weight and have SiO.sub.2/Al.sub.2O.sub.3
of 521 and Ni/Al of 0.12. Properties of the catalyst obtained are
set forth in Table 3.
(3) Oligomerization Reaction
[0130] Reaction was performed as described in Example 1 (3), except
that the catalyst obtained in (2) above was used. After the
reaction for 24 hours, the ethylene conversion was 21.7%, the
selectivity for butenes was 86.9%, and the selectivity for hexenes
was 8.4%. The catalyst life was 264 hours. The results are set
forth in Table 4.
Example 9
[0131] A fixed bed flow reactor (stainless steel, inner diameter:
9.5 mm, length: 250 mm) was used. The fixed bed flow reactor was
packed with 0.275 g of the catalyst obtained in Example 8 (2),
together with quartz wool and quartz sand as holding materials, so
that the total length of the packings became 250 mm. Nitrogen was
passed through the reactor at a rate of 50 ml/min at atmospheric
pressure, and the catalyst layer was held at 300.degree. C. for 2
hours. The gas flow was changed from nitrogen to ethylene, which
was fed at 300.degree. C., 0.35 MPa and WHSV of 6.67 h.sup.-1, and
thereby ethylene was oligomerized. After the reaction for 27.5
hours, the ethylene conversion was 37.7%, the selectivity for
butenes was 82.7%, and the selectivity for hexenes was 11.7%. The
catalyst life was 18 hours. The results are set forth in Table
4.
Example 10
(1) Preparation of Support
[0132] 3.0 g of Silica SS 62138 (manufactured by Saint-Gobain K.K.)
was suspended in 12 ml of distilled water, and 3 ml of an aqueous
solution containing 0.075 g of aluminum nitrate nonahydrate was
added to the suspension. The mixture was stirred at room
temperature for 10 minutes, and water was distilled away at
70.degree. C. under reduced pressure. The solid thus formed was
dried at 80.degree. C. in air for 3 hours and was calcined at
500.degree. C. for 6 hours to afford a support containing silica
and alumina.
(2) Preparation of Catalyst
[0133] 2.0 g of the support obtained in (1) above was suspended in
20 ml of distilled water. Subsequently, 20 ml of an aqueous
solution containing 0.0044 g of nickel nitrate hexahydrate was
added to the suspension, followed by stirring at room temperature
for 10 minutes and heating at 80.degree. C. for 20 hours. The
temperature was lowered to room temperature, and the solid formed
was filtered, washed with water, dried at 80.degree. C. in air for
3 hours, and calcined at 300.degree. C. for 6 hours to afford a
catalyst.
[0134] The catalyst was found to contain 0.035 wt % of nickel
relative to the support weight and have SiO.sub.2/Al.sub.2O.sub.3
of 470 and Ni/Al of 0.09. Properties of the catalyst obtained are
set forth in Table 3.
(3) Oligomerization Reaction
[0135] Reaction was performed as described in Example 1 (3), except
that the catalyst obtained in (2) above was used. After the
reaction for 24 hours, the ethylene conversion was 29.4%, the
selectivity for butenes was 86.7%, and the selectivity for hexenes
was 9.0%. The catalyst life was 72 hours. The results are set forth
in Table 4.
Example 11
(1) Preparation of Support
[0136] 5.0 g of Silica SS 62138 (manufactured by Saint-Gobain K.K.)
was suspended in 20 ml of distilled water, and 10 ml of an aqueous
solution containing 0.250 g of aluminum nitrate nonahydrate was
added to the suspension. The mixture was stirred at room
temperature for 10 minutes, and water was distilled away at
70.degree. C. under reduced pressure. The solid thus formed was
dried at 80.degree. C. in air for 3 hours and was calcined at
500.degree. C. for 6 hours to afford a support containing silica
and alumina.
(2) Preparation of Catalyst
[0137] 2.0 g of the support obtained in (1) above was suspended in
20 ml of distilled water. Subsequently, 20 ml of an aqueous
solution containing 0.0044 g of nickel nitrate hexahydrate was
added to the suspension, followed by stirring at room temperature
for 10 minutes and heating at 80.degree. C. for 20 hours. The
temperature was lowered to room temperature, and the solid formed
was filtered, washed with water, dried at 80.degree. C. in air for
3 hours, and calcined at 500.degree. C. for 6 hours to afford a
catalyst.
[0138] The catalyst was found to contain 0.043 wt % of nickel
relative to the support weight and have SiO.sub.2/Al.sub.2O.sub.3
of 275 and Ni/Al of 0.07. Properties of the catalyst obtained are
set forth in Table 3.
(3) Oligomerization Reaction
[0139] Reaction was performed as described in Example 9, except
that the catalyst obtained in (2) above was used. After the
reaction for 24 hours, the ethylene conversion was 45.2%, the
selectivity for butenes was 80.9%, and the selectivity for hexenes
was 13.1%. The catalyst life was 21 hours. The results are set
forth in Table 4.
Example 12
(1) Preparation of Support
[0140] 10.0 g of Silica SS 62138 (manufactured by Saint-Gobain
K.K.) was suspended in 40 ml of distilled water, and 10 ml of an
aqueous solution containing 0.50 g of aluminum nitrate nonahydrate
was added to the suspension. The mixture was stirred at room
temperature for 10 minutes, and water was distilled away at
70.degree. C. under reduced pressure. The solid thus formed was
dried at 80.degree. C. in air for 3 hours and was calcined at
500.degree. C. for 6 hours to afford a support containing silica
and alumina.
(2) Preparation of Catalyst
[0141] 8.8 g of the support obtained in (1) above was suspended in
88 ml of distilled water. Subsequently, 44 ml of an aqueous
solution containing 0.020 g of nickel nitrate hexahydrate was added
to the suspension, followed by stirring at room temperature for 10
minutes and heating at 80.degree. C. for 20 hours. The temperature
was lowered to room temperature, and the solid formed was filtered,
washed with water, dried at 80.degree. C. in air for 3 hours, and
calcined at 500.degree. C. for 6 hours to afford a catalyst.
[0142] The catalyst was found to contain 0.04 wt % of nickel
relative to the support weight and have SiO.sub.2/Al.sub.2O.sub.3
of 243 and Ni/Al of 0.06. Properties of the catalyst obtained are
set forth in Table 3.
(3) Oligomerization Reaction
[0143] A fixed bed flow reactor (stainless steel, inner diameter:
9.5 mm, length: 250 mm) was used. The fixed bed flow reactor was
packed with 0.275 g of the catalyst obtained in (2) above, together
with quartz wool and quartz sand as holding materials, so that the
total length of the packings became 250 mm. In this example,
nitrogen and hydrogen were used together for the pretreatment
before the reaction. In detail, nitrogen was passed through the
reactor at a rate of 50 ml/min at atmospheric pressure, and the
catalyst layer was held at 550.degree. C. for 1 hour. Subsequently,
a gas mixture containing 50% nitrogen and 50% hydrogen was passed
through the reactor at a rate of 100 ml/min at atmospheric
pressure, and the catalyst layer was held at 550.degree. C. for 0.5
hour. While the temperature of the catalyst layer was lowered,
nitrogen alone was passed at a rate of 50 ml/min at atmospheric
pressure. When the temperature of the catalyst layer became
300.degree. C., the gas flow was changed from nitrogen to ethylene,
which was fed at 300.degree. C., 0.35 MPa and WHSV of 6.67
h.sup.-1, and thereby ethylene was oligomerized. After the reaction
for 24 hours, the ethylene conversion was 44.1%, the selectivity
for butenes was 81.8%, and the selectivity for hexenes was 11.1%.
The catalyst life was 30 hours. The results are set forth in Table
4.
[0144] It was demonstrated that the pretreatment with hydrogen
increased the catalyst life while the activity was maintained.
TABLE-US-00003 TABLE 3 Amount of nickel SiO.sub.2/Al.sub.2O.sub.3
Ni/Al supported (wt %) (mol/mol) (mol/mol) Ex. 8 0.038 521 0.12 Ex.
9 0.038 521 0.12 Ex. 10 0.035 470 0.09 Ex. 11 0.043 275 0.07 Ex. 12
0.04 243 0.06
TABLE-US-00004 TABLE 4 Reac- Reac- Eth- Selec- Selec- tion tion
ylene tivity tivity temper- pres- con- for for ature sure WHSV
version butenes hexenes Life (.degree. C.) (MPa) (h.sup.-1) (%) (%)
(%) (h) Ex. 8 300 0.1 6.13 21.7 86.9 8.4 264 Ex. 9 300 0.35 6.67
37.7.sup.1) 82.7.sup.1) 11.7.sup.1) 18 Ex. 10 300 0.1 6.13 29.4
86.7 9.0 72 Ex. 11 300 0.35 6.67 45.2 80.9 13.1 21 Ex. 12 300 0.35
6.67 44.1 81.8 11.1 30 .sup.1)Date after the reaction for 27.5
hours
Example 13
[0145] A catalyst was prepared in the same manner as in Example 10,
except that the catalyst calcination time after the addition of
nickel nitrate hexahydrate was changed from 6 hours to 24 hours.
The catalyst was found to contain 0.035 wt % of nickel relative to
the support weight and have SiO.sub.2/Al.sub.2O.sub.3 of 470 and
Ni/Al of 0.09.
[0146] Reaction was performed as described in Example 11, except
that the above catalyst was used. After the reaction for 24 hours,
the ethylene conversion was 38.7%, the selectivity for butenes was
82.0%, and the selectivity for hexenes was 12.2%. The catalyst life
was 50 hours. The results are set forth in Table 6.
Example 14
[0147] A catalyst was prepared in the same manner as in Example 13,
except that the catalyst calcination time was changed from 24 hours
to 60 hours. The catalyst was found to contain 0.035 wt % of nickel
relative to the support weight and have SiO.sub.2/Al.sub.2O.sub.3
of 470 and Ni/Al of 0.09.
[0148] Reaction was performed as described in Example 11, except
that the above catalyst was used. After the reaction for 24 hours,
the ethylene conversion was 35.6%, the selectivity for butenes was
83.2%, and the selectivity for hexenes was 11.2%. The catalyst life
was 50 hours. The results are set forth in Table 6.
[0149] The results of Examples 13 and 14 showed that the catalysts
achieved an increased catalyst life when calcined for 24 hours or
more while the catalytic activity was maintained.
TABLE-US-00005 TABLE 5 Reac- Reac- Eth- Selec- Selec- tion tion
ylene tivity tivity temper- pres- con- for for ature sure WHSV
version butenes hexenes Life (.degree. C.) (MPa) (h.sup.-1) (%) (%)
(%) (h) Ex. 11 300 0.35 6.67 45.2 80.9 13.1 21 Ex. 13 300 0.35 6.67
38.7 82.0 12.2 50 Ex. 14 300 0.35 6.67 35.6 83.2 11.2 50
Example 15
[0150] The catalyst used in Example 14 was regenerated by passing a
gas mixture containing 96% nitrogen and 4% oxygen at a rate of 45
ml/min under atmospheric pressure at 500.degree. C. for 2 hours.
The regenerated catalyst was used to catalyze a reaction similarly
to Example 14. The regenerated catalyst maintained a performance
equivalent to that before the regeneration even when it was
regenerated three times. This result showed that the catalysts
according to the present invention were regeneratable.
Example 16
(1) Preparation of Support
[0151] 5.0 g of Sylosphere 1504 (manufactured by FUJI SILYSIA
CHEMICAL LTD.) was suspended in 20 ml of distilled water, and 5 ml
of an aqueous solution containing 0.125 g of aluminum nitrate
nonahydrate was added to the suspension. The mixture was stirred at
room temperature for 10 minutes, and water was distilled away at
70.degree. C. under reduced pressure. The solid thus formed was
dried at 80.degree. C. in air for 3 hours and was calcined at
500.degree. C. for 6 hours to afford a support containing silica
and alumina.
(2) Preparation of Catalyst
[0152] 2.0 g of the support obtained in (1) above was suspended in
20 ml of distilled water. Subsequently, 20 ml of an aqueous
solution containing 0.0044 g of nickel nitrate hexahydrate was
added to the suspension, followed by stirring at room temperature
for 10 minutes and heating at 80.degree. C. for 20 hours. The
temperature was lowered to room temperature, and the solid formed
was filtered, washed with water, dried at 80.degree. C. in air for
3 hours, and calcined at 300.degree. C. for 6 hours to afford a
catalyst.
[0153] The catalyst was found to contain 0.043 wt % of nickel
relative to the support weight and have SiO.sub.2/Al.sub.2O.sub.3
of 521 and Ni/Al of 0.14.
(3) Oligomerization Reaction
[0154] Reaction was performed as described in Example 1 (3), except
that the catalyst obtained in (2) above was used. After the
reaction for 24 hours, the ethylene conversion was 24.1%, the
selectivity for butenes was 85.8%, and the selectivity for hexenes
was 9.4%. The catalyst life was 71 hours. The results are set forth
in Table 6.
Example 17
[0155] Reaction was performed as described in Example 1 (3), except
that the catalyst obtained in Example 16 (2) was used and that the
reaction pressure was changed from 0.1 MPa to 0.2 MPa. After the
reaction for 24 hours, the ethylene conversion was 36.3%, the
selectivity for butenes was 83.5%, and the selectivity for hexenes
was 10.8%. The catalyst life was 60 hours. The results are set
forth in Table 6.
Example 18
[0156] Reaction was performed as described in Example 1 (3), except
that the catalyst obtained in Example 16 (2) was used and that the
reaction pressure was changed from 0.1 MPa to 0.35 MPa. After the
reaction for 24 hours, the ethylene conversion was 49.5%, the
selectivity for butenes was 79.4%, and the selectivity for hexenes
was 13.5%. The catalyst life was 24 hours. The results are set
forth in Table 6.
Example 19
[0157] Reaction was performed as described in Example 1 (3), except
that the catalyst obtained in Example 16 (2) was used and that the
reaction temperature was changed from 300.degree. C. to 250.degree.
C. After the reaction for 24 hours, the ethylene conversion was
29.2%, the selectivity for butenes was 87.8%, and the selectivity
for hexenes was 9.2%. The catalyst life was 88 hours. The results
are set forth in Table 6.
Example 20
[0158] Reaction was performed as described in Example 1 (3), except
that the catalyst obtained in Example 16 (2) was used and that the
reaction temperature was changed from 300.degree. C. to 200.degree.
C. After the reaction for 24 hours, the ethylene conversion was
13.2%, the selectivity for butenes was 92.3%, and the selectivity
for hexenes was 6.6%. The catalyst life was 163 hours. The results
are set forth in Table 6.
Example 21
[0159] Reaction was performed as described in Example 1 (3), except
that the catalyst obtained in Example 16 (2) was used and that the
WHSV was changed from 6.13 h.sup.-1 to 10.7 h.sup.-1. After the
reaction for 24 hours, the ethylene conversion was 24.5%, the
selectivity for butenes was 85.1%, and the selectivity for hexenes
was 9.6%. The catalyst life was 69 hours. The results are set forth
in Table 6.
Example 22
[0160] Reaction was performed as described in Example 1 (3), except
that the catalyst obtained in Example 16 (2) was used and that the
WHSV was changed from 6.13 h.sup.-1 to 21.4 h.sup.-1. After the
reaction for 24 hours, the ethylene conversion was 26.7%, the
selectivity for butenes was 85.3%, and the selectivity for hexenes
was 10.3%. The catalyst life was 72 hours. The results are set
forth in Table 6.
Example 23
[0161] Reaction was performed as described in Example 1 (3), except
that the catalyst obtained in Example 16 (2) was used, that the
reaction pressure was changed from 0.1 MPa to 0.35 MPa, and that
the WHSV was changed from 6.13 h.sup.-1 to 2.05 h.sup.-1. After the
reaction for 24 hours, the ethylene conversion was 21.7%, the
selectivity for butenes was 91.1%, and the selectivity for hexenes
was 7.3%. The catalyst life was 124 hours. The results are set
forth in Table 6.
[0162] Changes with time of ethylene conversion and selectivity for
butenes are shown in FIG. 1.
TABLE-US-00006 TABLE 6 Reac- Reac- Eth- Selec- Selec- tion tion
ylene tivity tivity temper- pres- con- for for ature sure WHSV
version butenes hexenes Life (.degree. C.) (MPa) (h.sup.-1) (%) (%)
(%) (h) Ex. 16 300 0.1 6.13 24.1 85.8 9.4 71 Ex. 17 300 0.2 6.13
36.3 83.5 10.8 60 Ex. 18 300 0.35 6.13 49.5 79.4 13.5 24 Ex. 19 250
0.35 6.13 29.2 87.8 9.2 88 Ex. 20 200 0.35 6.13 13.2 92.3 6.6 163
Ex. 21 300 0.35 10.7 24.5 85.1 9.6 69 Ex. 22 300 0.35 21.4 26.7
85.3 10.3 72 Ex. 23 200 0.35 2.05 21.7 91.1 7.3 124
Example 24
(1) Preparation of Support
[0163] 5.0 g of Sylosphere 1504 (manufactured by FUJI SILYSIA
CHEMICAL LTD.) was suspended in 20 ml of distilled water, and 5 ml
of an aqueous solution containing 0.063 g of aluminum nitrate
nonahydrate was added to the suspension. The mixture was stirred at
room temperature for 10 minutes, and water was distilled away at
70.degree. C. under reduced pressure. The solid thus formed was
dried at 80.degree. C. in air for 3 hours and was calcined at
500.degree. C. for 6 hours to afford a support containing silica
and alumina.
(2) Preparation of Catalyst
[0164] 2.0 g of the support obtained in (1) above was suspended in
20 ml of distilled water. Subsequently, 20 ml of an aqueous
solution containing 0.044 g of nickel nitrate hexahydrate was added
to the suspension, followed by stirring at room temperature for 10
minutes and heating at 80.degree. C. for 20 hours. The temperature
was lowered to room temperature, and the solid formed was filtered,
washed with water, dried at 80.degree. C. in air for 3 hours, and
calcined at 300.degree. C. for 6 hours to afford a catalyst.
[0165] The catalyst was found to contain 0.09 wt % of nickel
relative to the support weight and have SiO.sub.2/Al.sub.2O.sub.3
of 1041 and Ni/Al of 0.58.
(3) Oligomerization Reaction
[0166] Reaction was performed as described in Example 1 (3), except
that the catalyst obtained in (2) above was used. After the
reaction for 24 hours, the ethylene conversion was 20.5%, the
selectivity for butenes was 86.4%, and the selectivity for hexenes
was 8.9%. The catalyst life was 33 hours.
Example 25
(1) Preparation of Support
[0167] An autoclave was charged with a solution of 112.5 g of
n-dodecyltrimethylammonium bromide in 321 ml of distilled water, a
solution of 5.30 g of sodium hydroxide in 63 ml of distilled water,
and 153.15 g of SNOWTEX 20 (manufactured by NISSAN CHEMICAL
INDUSTRIES, LTD.). These materials were heated to 140.degree. C.
and stirred for 48 hours, and the temperature was lowered to room
temperature. The solid thus formed was filtered, washed with water,
and dried at 80.degree. C. in air for 24 hours to afford 45.51 g of
a support containing silica and alumina.
(2) Preparation of Catalyst
[0168] 8.0 g of the support obtained in (1) above was suspended in
80 ml of distilled water. Subsequently, 80 ml of an aqueous
solution containing 0.025 g of nickel nitrate hexahydrate was added
to the suspension, followed by stirring at room temperature for 1
hour and heating at 80.degree. C. for 20 hours. The temperature was
lowered to room temperature, and the solid formed was filtered,
washed with water, dried at 80.degree. C. in air for 3 hours, and
calcined at 500.degree. C. for 6 hours to afford a catalyst.
[0169] The catalyst was found to contain 0.09 wt % of nickel
relative to the support weight and have SiO.sub.2/Al.sub.2O.sub.3
of 400 and Ni/Al of 0.24. Properties of the catalyst obtained are
set forth in Table 7.
(3) Oligomerization Reaction
[0170] Reaction was performed as described in Example 1 (3), except
that the catalyst obtained in (2) above was used and that the
reaction temperature was changed to 350.degree. C. After the
reaction for 24 hours, the ethylene conversion was 45.3%, the
selectivity for butenes was 74.5%, and the selectivity for hexenes
was 11.0%. The catalyst life was 341 hours. The results are set
forth in Table 8.
TABLE-US-00007 TABLE 7 Amount of nickel SiO.sub.2/Al.sub.2O.sub.3
Ni/Al supported (wt %) (mol/mol) (mol/mol) Ex. 25 0.09 400 0.24
TABLE-US-00008 TABLE 8 Reac- Reac- Eth- Selec- Selec- tion tion
ylene tivity tivity temper- pres- con- for for ature sure WHSV
version butenes hexenes Life (.degree. C.) (MPa) (h.sup.-1) (%) (%)
(%) (h) Ex. 25 350 0.1 6.13 45.3 74.5 11.0 341
Example 26
(1) Preparation of Support
[0171] 20.12 g of CARIACT Q-10 (manufactured by FUJI SILYSIA
CHEMICAL LTD.) was suspended in 80 ml of distilled water, and 20 ml
of an aqueous solution containing 0.502 g of aluminum nitrate
nonahydrate was added to the suspension. Water was removed, and the
resultant solid was dried at 80.degree. C. for 3 hours and was
calcined at 500.degree. C. for 6 hours to afford a support
containing silica and alumina.
(2) Preparation of Catalyst
[0172] 2.0 g of the support obtained in (1) above was suspended in
20 ml of distilled water. Subsequently, 0.5 ml of an aqueous
solution prepared by dissolving 0.0042 g of nickel nitrate
hexahydrate in 20 ml of distilled water was added to the
suspension. Further, 20 ml of distilled water was added, followed
by stirring. The mixture was heated at 80.degree. C. for 20 hours.
The solid formed was filtered, washed with water, dried at
80.degree. C. for 3 hours, and calcined at 500.degree. C. for 6
hours to afford a catalyst.
[0173] The catalyst was found to contain 0.001 wt % of nickel
relative to the support weight and have SiO.sub.2/Al.sub.2O.sub.3
of 439 and Ni/Al of 0.0023. Properties of the catalyst obtained are
set forth in Table 9.
(3) Oligomerization Reaction
[0174] 0.279 g of the catalyst obtained in (2) above was packed in
a fixed bed flow reactor. Nitrogen was passed through the reactor
at a rate of 50 ml/min at atmospheric pressure, and the catalyst
layer was held at 300.degree. C. for 2 hours. The gas flow was
changed from nitrogen to ethylene, which was fed at 250.degree. C.,
3.6 MPa and WHSV of 2.15 h.sup.-1, and thereby ethylene was
oligomerized. After the reaction for 29 hours, the ethylene
conversion was 39.7%, the selectivity for butenes was 86.6%, and
the selectivity for hexenes was 11.2%. The catalyst life was 83
hours. The results are set forth in Table 10.
Example 27
[0175] Reaction was performed as described in Example 26 (3),
except that the catalyst obtained in Example 26 (2) was used and
that the reaction temperature was changed from 250.degree. C. to
300.degree. C. and the WHSV was changed from 2.15 h.sup.-1 to 6.67
h.sup.-1. After the reaction for 26 hours, the ethylene conversion
was 45.0%, the selectivity for butenes was 84.7%, and the
selectivity for hexenes was 12.1%. The catalyst life was 68 hours.
The results are set forth in Table 10.
Example 28
(1) Preparation of Catalyst
[0176] 1.0 g of the support obtained in Example 10 (1) was
suspended in 10 ml of distilled water. Subsequently, 0.5 ml of an
aqueous solution prepared by dissolving 0.0018 g of nickel sulfate
hexahydrate in 40 ml of distilled water was added to the
suspension. Further, 10 ml of distilled water was added, followed
by stirring. Water was distilled away, and the residue was dried at
80.degree. C. for 3 hours and was calcined at 500.degree. C. for 6
hours to afford a catalyst.
[0177] The catalyst was found to contain 0.001 wt % of nickel
relative to the support weight and have SiO.sub.2/Al.sub.2O.sub.3
of 470 and Ni/Al of 0.0024. Properties of the catalyst obtained are
set forth in Table 9.
(2) Oligomerization Reaction
[0178] Reaction was performed as described in Example 27 using
0.279 g of the catalyst obtained in (1) above. After the reaction
for 26 hours, the ethylene conversion was 36.5%, the selectivity
for butenes was 88.8%, and the selectivity for hexenes was 9.5%.
The catalyst life was 45 hours. The results are set forth in Table
10.
Example 29
(1) Preparation of Catalyst
[0179] 2.1 g of the support obtained in Example 11 (1) was
suspended in 20 ml of distilled water. Subsequently, 0.5 ml of an
aqueous solution prepared by dissolving 0.0041 g of nickel nitrate
hexahydrate in 40 ml of distilled water was added to the
suspension. Further, 20 ml of distilled water was added, followed
by stirring. The mixture was heated at 80.degree. C. for 20 hours.
The solid formed was filtered, washed with water, dried at
80.degree. C. for 3 hours, and calcined at 500.degree. C. for 6
hours to afford a catalyst.
[0180] The catalyst was found to contain 0.0005 wt % of nickel
relative to the support weight and have SiO.sub.2/Al.sub.2O.sub.3
of 275 and Ni/Al of 0.0007. Properties of the catalyst obtained are
set forth in Table 9.
(2) Oligomerization Reaction
[0181] Reaction was performed as described in Example 27, except
that 0.574 g of the catalyst obtained in (1) above was used and
that the WHSV was changed from 6.67 h.sup.-1 to 1.0 h.sup.-1. After
the reaction for 26 hours, the ethylene conversion was 35.8%, the
selectivity for butenes was 73.9%, and the selectivity for hexenes
was 15.4%. The catalyst life was 39 hours. The results are set
forth in Table 10.
Comparative Example 5
[0182] Reaction was performed as described in Example 27, except
that the catalyst from Example 26 (1) was used without supporting
nickel. At an initial stage of the reaction, the ethylene
conversion was 0%, the selectivity for butenes was 0%, and the
selectivity for hexenes was 0%. The reaction was continued for 20
hours thereafter, but the ethylene conversion, the selectivity for
butenes and the selectivity for hexenes were all 0%. The results
are set forth in Table 10.
Comparative Example 6
(1) Preparation of Support
[0183] 5.00 g of CARIACT Q-10 (manufactured by FUJI SILYSIA
CHEMICAL LTD.) was suspended in 20 ml of distilled water, and 20 ml
of an aqueous solution containing 0.125 g of aluminum nitrate
nonahydrate was added to the suspension. Water was removed, and the
resultant solid was dried at 80.degree. C. for 3 hours and was
calcined at 500.degree. C. for 6 hours to afford a support
containing silica and alumina.
(2) Preparation of Catalyst
[0184] 1.1 g of the support obtained in (1) above was suspended in
10 ml of distilled water. Subsequently, an aqueous solution of
0.136 g of nickel nitrate hexahydrate in 40 ml of distilled water
was added to the suspension, followed by stirring. Water was
removed, and the resultant solid was dried at 80.degree. C. for 3
hours and was calcined at 300.degree. C. for 6 hours to afford a
catalyst.
[0185] The catalyst was found to contain 1.6 wt % of nickel
relative to the support weight and have SiO.sub.2/Al.sub.2O.sub.3
of 576 and Ni/Al of 5.66. Properties of the catalyst obtained are
set forth in Table 9.
(3) Oligomerization Reaction
[0186] 0.279 g of the catalyst obtained in (2) above was packed in
a fixed bed flow reactor, and reaction was performed as described
in Example 27. After the reaction for 1.5 hours, the ethylene
conversion was 86.7%, the selectivity for butenes was 50.5%, and
the selectivity for hexenes was 11.0%. The catalyst showed the high
ethylene conversion at the initial stage of reaction, but the
catalyst life was only 7 hours. The results are set forth in Table
10.
[0187] It was demonstrated that increasing the amount of nickel
supported provided high activity at an initial stage of the
reaction, but the catalyst was deactivated quickly and could not
ensure stable productivity over long periods.
TABLE-US-00009 TABLE 9 Amount of nickel SiO.sub.2/Al.sub.2O.sub.3
Ni/Al supported (wt %) (mol/mol) (mol/mol) Ex. 26 0.001 439 0.0023
Ex. 27 0.001 439 0.0023 Ex. 28 0.001 470 0.0024 Ex. 29 0.0005 275
0.0007 Comp. 0 439 0 Ex. 5 Comp. 1.6 576 5.66 Ex. 6
TABLE-US-00010 TABLE 10 Reac- Reac- Eth- Selec- Selec- tion tion
ylene tivity tivity temper- pres- con- for for ature sure WHSV
version butenes hexenes Life (.degree. C.) (MPa) (h.sup.-1) (%) (%)
(%) (h) Ex. 26 250 3.6 2.15 39.7.sup.1) 86.6.sup.1) 11.2.sup.1) 83
Ex. 27 300 3.6 6.67 45.0.sup.2) 84.7.sup.2) 12.1.sup.2) 68 Ex. 28
300 3.6 6.67 36.5.sup.2) 88.8.sup.2) 9.5.sup.2) 45 Ex. 29 300 3.6
1.0 35.8.sup.2) 73.9.sup.2) 15.4.sup.2) 39 Comp. 300 3.6 6.67
0.sup.3) 0.sup.3) 0.sup.3) 0 Ex. 5 Comp. 300 3.6 6.67 86.7.sup.4)
50.5.sup.4) 11.0.sup.4) 7 Ex. 6 .sup.1)Date after the reaction for
29 hours .sup.2)Data after the reaction for 26 hours .sup.3)Data
after the reaction for 20 hours .sup.4)Data after the reaction for
1.5 hours
Example 30
[0188] In this example, an oligomerization reaction and a
disproportionation reaction were carried out in a single
reactor.
[0189] The catalyst from Example 26 (2) was used as an
oligomerization catalyst. Tungsten oxide supported on silica was
used as a disproportionation catalyst. The disproportionation
catalyst was prepared according to the preparation of Catalyst
component A in Example 1 of U.S. Pat. No. 4,575,575. A fixed bed
flow reactor was packed with 0.28 g of the oligomerization catalyst
and a catalyst mixture consisting of 0.33 g of the
disproportionation catalyst and 0.99 g of magnesium oxide
(hereinafter, also the disproportionation catalyst/cocatalyst),
together with quartz wool and quartz sand as holding materials, so
that the total length of the packings became 400 mm.
[0190] The oligomerization catalyst and the disproportionation
catalyst/cocatalyst were activated by the method described in
Example 3 of U.S. Pat. No. 4,575,575 except that hydrogen was used
in place of carbon monoxide. The gas flow to the reactor was
changed to ethylene at WHSV of 8.9 h.sup.-1 relative to the
oligomerization catalyst, and thereby ethylene was brought into
contact with the oligomerization catalyst and oligomerized at
350.degree. C. and 2.86 MPa. Successively, the oligomer from the
oligomerization was brought into contact with ethylene in the
presence of the disproportionation catalyst/cocatalyst and was
thereby disproportionated.
[0191] After the reaction for 29 hours, the ethylene conversion was
56.4% and the propylene selectivity was 62.4%. After the reaction
for 59 hours, the ethylene conversion was 50.1% and the propylene
selectivity was 50.2%. The results of Example 30 show that
propylene can be produced stably over a long period with little
deterioration of the catalyst according to the present
invention.
[0192] In the case where by-produced olefins such as butene other
than the raw material ethylene and the product propylene are all
recycled, the propylene selectivity reaches 97% or more. It is
possible to produce propylene with higher selectivity.
* * * * *